Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/046—Insoluble free body dispenser
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
  • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
  • B65D1/04—Multi-cavity bottles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
  • B65D1/32—Containers adapted to be temporarily deformed by external pressure to expel contents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
  • B65D81/3283—Cylindrical or polygonal containers, e.g. bottles, with two or more substantially axially offset, side-by-side compartments for simultaneous dispensing
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means

Definitions

• Dispenser bottle for at least two active fluids
• the invention relates to a dispenser bottle with at least two receptacles for active substance fluids that can thus be stored separately from one another, with the features of the preamble of claim 1.
• active fluids which should or must be stored separately from one another. These active ingredient fluids should only meet shortly before or when they are applied to the application area, for example a floor, the surface of a toilet bowl, etc. Examples of these are chlorine-containing bleaching agents, cleaning agents, decalcifying agents and disinfectants (e.g. WO 98/21308 A2). Active fluids of the type in question are also applied, for example, to surfaces in the bathroom or in other hygienically sensitive areas.
• Active agent fluids are stored in different receptacles, especially when together they are not stable in storage.
• other reasons for separate storage of active substance fluids which are to be applied together are also known, for example different colors which are intended to communicate different functions of the active substance fluids, different light sensitivities etc.
• the dispenser bottle for at least two different active substance fluids that are not stable with one another and from which the invention is based has two separate fluids Chambers, which form the receptacles, have a bottle which is provided at the upper end with immediately adjacent outlets for the active substance fluids in the two receptacles.
• the concentration of the components in the two aqueous solutions is chosen such that when a certain amount of the first aqueous solution is mixed with a certain amount of the second aqueous solution, the acid bleaching solution desired in this prior art is the result ,
• the dispenser bottle of the prior art explained above, which forms the starting point, has a pump device which can be placed on the outlets of the two receiving containers of the dispenser bottle.
• the active substance fluids are brought together and ejected from a discharge nozzle in a common spray jet, ie the active substance fluids are mixed with one another before they leave the discharge nozzle.
• a similar dispenser bottle in which cross contamination between the two receptacles can largely be avoided, is also known (WO 91/04923 A1; DE 690 16 44 T2). With this dispenser bottle, no pump spray device is provided, but the outlets are simply open and can be provided with spouts be closed again by means of a sealing cap. However, this dispenser bottle is not suitable for a spray application.
• a dispenser bottle for an active substance fluid with a receptacle made of flexible plastic and an ejection nozzle is known specifically for cleaning toilet bowls (EP 0 911 616 B1), with the ejection nozzle for optimal application of the active substance fluid in the toilet bowl, in particular under its inner edge is designed as an angled metering tube.
• a liquid detergent is known from international patent application WO 00/11713 A1, which consists of at least two liquid partial compositions, the active substance fluids being stored separately from one another in a container with at least two chambers (receiving containers) and at least one of which is an imine or Oxaziridine bleach activator and at least one other has an alkalizing agent, at least one of the sub-compositions containing a peroxygen bleach and each sub-composition having a pH value leading to stability.
• the alkalizing agent increases the pH of the final composition, so that bleach and bleach activator react effectively with one another.
• a dispenser with two chambers is known from European patent EP 0 807 156 B1, the first chamber of which contains an aqueous composition of hydrogen peroxide or an organic peracid with a pH value above 2 and below 7 and the second chamber of which contains an acidic component and from which the contents are collected together or released one after the other on a surface in such a way that the resulting mixture has a pH of at most 2.
• German patent application DE 100 24 251 A1 proposes a bleaching agent which, in a first component, consists of an aqueous 1 to 40 percent by weight aqueous imidoperoxocarboxylic acid dispersion and in a second component consists of a mixture of substances activating the first component, separately in one Keep the double-chamber bottle and only mix the two components when using it.
• the second component also referred to in this publication as pH-regulating buffer solution, consists of an aqueous solution of sodium hydrogen carbonate and sodium carbonate, which has been thickened with the aid of methyl cellulose.
• the teaching is now based on the problem of specifying a dispenser bottle with at least two receptacles for two active fluids, which can be manufactured inexpensively and is easy to handle by an operator and which allows two active substance fluids to be applied separately from one another but in one application field.
• the receptacles are preferably designed as compressible containers. By squeezing the receptacles by the hand of an operator, the necessary internal pressure is generated in the receptacles to expel the active substance fluids from the discharge nozzles provided separately.
• the required pressure can also be generated by gravity if the product delivery is not carried out upwards against the force of gravity, such as in the toilet, but downwards, such as when applying cleaning agents for floor cleaning or putting detergents into the washing machine.
• the active agent fluids therefore only mix after leaving the ejection nozzles in the application field.
• the desired product to be applied in particular the cleaning agent, bleaching agent, etc., which has the desired effect in the application field, is created during the application from the two active fluid.
• the claimed dispenser bottle achieves the previously explained result with a structurally very simple and easy-to-use solution, in particular without a pump spray device.
• the claimed dispenser bottle is therefore ideally suited for use as a mass product, in particular for cleaning agents of all kinds, in particular also for toilet cleaning.
• the claimed dispenser bottle can also be used for a large number of other applications, for example for the metering of textile cleaning agents (detergents in washing machines etc.), textile pre-treatment agents (bleaching agents etc.), textile post-treatment agents (fabric softener etc.), for the metering of manual and machine dishwashing detergents and dishwashing aids (rinse aid, lime remover, etc.), and finally for the dosing of surface cleaning agents and surface treatment agents of all kinds.
• Active substance fluids in the sense of the teaching of the present patent application are to be understood to mean all liquid and other flowable media, from thin to viscous to gel-like to paste-like substances. Powdery and lumpy as well as granular active substances can also be applied with the dispenser bottle according to the invention.
• the viscosity of the active substance fluids or the flowability of the active substances is important for the application of interest, on the other hand, and in a particular way, the thixotropy of the active substance fluids is also important (for explaining the term thixotropy, the phenomenon that certain active substance fluids are present Liquefy the action of mechanical forces, but after the mechanical stress has ended, if necessary solidify again after a considerable time delay, i.e. have a viscosity dependent on the action of mechanical forces, see R ⁇ MPP LEXIKON Chemie, 10th edition, Georg Thieme Verlag, Stuttgart, 1999, volume 6, page 4533).
• the cross-sectional constrictions are arranged on the mutually facing sides of the nozzle channels in such a way that the active substance fluids emerging under pressure have a swirl directed towards one another.
• the application field of the application area can then be located here. This configuration with the narrowing of the cross section is particularly important when the active substance fluids are essentially thixotropic active substance fluids of the same type.
• the swirl effect is also produced when the openings of the nozzle channels of the ejection nozzles are bevelled relative to one another, ie the opening planes of the nozzle channels are at an angle to one another, the section of the wall of the ejection nozzle lying inside the longitudinal axis of the nozzle channel being longer than the section lying outside the longitudinal axis of the nozzle channel Section of the wall.
• FIG. 1a is a perspective view of a first embodiment of a dispenser bottle according to the invention
• FIG. 1b is a perspective view of a second embodiment of a dispenser bottle according to the invention.
• FIG. 3 shows the dispenser bottle from FIG. 1 a in a representation corresponding to FIG. 2 a, but without a nozzle head
• FIG. 7 shows the dosing head of the dispenser bottle from FIG. 6 in a side view
• FIG. 9 shows the dosing head from FIG. 7 in a section perpendicular to the section from FIG. 8,
• FIG. 10 shows the dosing head in a representation corresponding to FIG. 9, now with the closure cap attached
• 11b shows the spray pattern of the active substance fluids in a second exemplary embodiment of a dispenser bottle according to the invention
• FIG. 12 shows the spray pattern of the active substance fluids in a further exemplary embodiment of a dispenser bottle according to the invention
• Fig. 12a the metering channel in section at the level of the cross-sectional constriction in a further embodiment and 12b corresponding to the Dösierkanal in a third embodiment
• FIG. 14 is a dispenser bottle with a cap according to. Fig. 13.
• the invention relates to a dispenser bottle as shown in perspective in FIGS. 1a and 1b and laterally in FIGS. 2a and 2b.
• a first receptacle 1 for a first active fluid can be seen on the left and a second receptacle 2 for a second active fluid can be seen on the right.
• more than two receptacles 1, 2 can also be provided, for example three receptacles for three active fluids or even four receptacles for four active fluids which are intended to meet in the application area.
• the active substance fluids will often be active substance fluids that are not stable with one another; however, this is not a mandatory requirement for the teaching of the invention. Reference may be made to the explanations above. Likewise, reference may be made to the statements made above with regard to the definition of the term “active substance fluid” in the sense of this patent application and the special, preferred properties of such active substance fluids.
• the two receptacles 1, 2 are either designed separately and connected to one another, for example by gluing or latching. which is another connecting element or, as in the illustrated embodiment, made in one piece with one another.
• gluing or latching which is another connecting element or, as in the illustrated embodiment, made in one piece with one another.
• a dispenser bottle is preferred in which the two receptacles 1, 2 are made in one piece. This will be explained later.
• FIGS. 3 and 4 show the receptacles 1, 2 for the first embodiment of the dispenser bottle according to FIGS. 1a and 2a separately. It can be seen that the receptacles each have an outlet 3, 4 for the respective active fluid. The outlets 3, 4 are arranged adjacent to one another in such a way that the two active substance fluids can be applied in a common application field 5, indicated in FIG. 11, of a larger application area.
• the general importance of this external mixing of the active substance fluids from the two receptacles 1, 2 has been pointed out in detail in the general part of the description; reference may be made to this.
• the receptacles were not shown separately, the only difference would be that they do not have a holding area, since the application takes place by pivoting and the liquid escapes due to gravity.
• the dispenser bottle according to the invention is always explained as if there were only two receptacles 1, 2 for two active agent fluids.
• the statement explained at the beginning that several receptacles can also be used must be remembered because the explanations should also apply to such multi-container dispenser bottles.
• the receptacles 1, 2 are each provided with an outlet 3, 4 each with at least one, preferably with exactly one ejection nozzle 6, 7, so that the active substance fluids only come together after they have left the ejection nozzles 6, 7 be mixed.
• the receptacles 1, 2 are designed as compressible containers, since they are preferably used for product delivery against gravity as for dosing under the toilet rim.
• the ejection nozzles 6, 7 are preferably inclined with respect to the longitudinal axis of the receptacles 1, 2.
• the dispenser bottle according to the second embodiment FIG. 2
• the ejection nozzles 6, 7 run parallel in the direction of the longitudinal axis of the receptacles 1, 2, since with this dispenser bottle preferably detergent into the washing-up chamber of a washing machine or a dosing aid for the Drum of a washing machine or detergent can be applied directly to the surface to be cleaned by gravitational force.
• the receptacles 1, 2 can be designed as compressible containers.
• the ejection nozzles 6, 7 can first be seen in FIGS. 6 a and 6 b, otherwise also in FIG. 8 and shown schematically in FIGS. 11 a, b.
• the pressure for pressing the active substance fluids out of the receptacles 1, 2 is applied by the hand of an operator or by gravity after giving away by more than 90 °.
• the active substance fluids leave the ejection nozzles 6, 7 to which they flow from the outlets 3, 4 of the two receptacles 1, 2. Only after leaving the ejection nozzles 6, 7, depending on the pressure exerted by the operator, does the clash occur at a certain distance Streams of the active ingredient fluids and their mixing to the product to be used in the application area.
• the illustrated and preferred exemplary embodiment according to FIGS. 1 a, 2 a further shows that the receptacles 1, 2 consist of a material with a resetting characteristic and / or have a shape that supports resetting into the original shape.
• a material for the receptacle 1, 2 can be, for example, a polyolefin, in particular a polypropylene (PP), a polyethylene (PE), a polyvinyl chloride (PVC) or a polyethylene terephthalate (PET), in particular a glycol-modified one Polyethylene terephthalate (PETG).
• PP polypropylene
• PE polyethylene
• PVC polyvinyl chloride
• PET polyethylene terephthalate
• PETG glycol-modified one Polyethylene terephthalate
• Typical volumes of receptacles 1, 2 in the area of application of the household are between 50 ml and 1,500 ml, a preferred range between 300 ml and 500 ml for each of the receptacles 1, 2. Of course, this is application-specific and depends on the active fluid.
• FIGS. 1a and 1b show in particular in FIG. 4, but also in FIGS. 6a and 6b, that the receptacles 1, 2 are designed as complete containers and only have at least one, preferably exactly one, between the containers Receptacles 1, 2 formed connecting web 8 are interconnected.
• the connecting web 8 is preferably integrally formed on the mutually facing inner sides of the receptacles 1, 2, in particular, for example, molded simultaneously with the receptacles 1, 2 in the blow molding process. It is particularly expedient if the connecting web 8 is arranged approximately in the middle and extends iw - possibly with interruptions - over the full length of the receptacles 1, 2.
• the connecting web 8 thus forms a stiffening element for the mutually facing walls of the receptacles 1, 2, stabilizes them and at the same time leads to the design of a Abutment for the pressure forces exerted by the operator's hand.
• the receptacles 1, 2 should together have a cross section such that they can be largely encompassed by an operator's hand.
• the blow molding process has already been mentioned previously as an expedient method for producing the receptacles 1, 2.
• the receptacles 1, 2, which are made in one piece with one another have a different light transmittance and / or a different coloring.
• active fluids are sensitive to light.
• Other drug fluids to be applied in conjunction with the respective drug fluid are less sensitive to light.
• An opaque coloring of the receptacle provided for the more light-sensitive active fluid eliminates problems here.
• the dispenser bottle shown in the drawings according to FIGS. 1a, 2a is further characterized in that a holding area 9 to be encompassed by the hand of an operator is provided on the receiving containers 1, 2 by special edge configurations 10, 11 and / or Surface designs is formed and / or marked. This can be seen particularly well in FIGS. 1 and 2.
• the recessed grip literally entices to grip the dispenser bottle by hand from here.
• the dispenser bottle has a specific position with respect to the operator's hand, which is defined by the edge 10.11 is specified.
• surface designs for example, corrugations, other colors, etc. are also possible.
• the receptacles 1, 2 With regard to the dimensions, it has proven to be expedient not to let the receptacles 1, 2 become too large in order not to hinder the manageability. Preferred dimensions result in such a way that the receptacles 1, 2 in cross section in the holding area 9 to be encompassed by the hand of an operator have an outer circumference of approx. 18 to approx. 30 cm, preferably of approx. 20 to approx. 28 cm, in particular of approx 22 to approx. 26 cm, in particular of approx. 24 cm.
• active ingredient fluids With regard to the viscosity of the active ingredient fluids, it is recommended to use active ingredient fluids with viscosities in the range from 1 to 100,000 mPas. preferably up to about 10,000 mPas, in particular up to about 1,000 mPas. This information is based on the viscosity measured with a Brookfield LVT-II viscometer at 20 rpm. and 20 ° C, spindle 3.
• Aqueous solutions of the type already mentioned in the general part of the description are likely to be used frequently (see also US 5,911, 909 A and US 5,972,239 A, the disclosure content of which is also incorporated into the disclosure content of the present patent application by reference). It has already been indicated above that it can be of particular importance for the teaching of the present invention if at least one of the active substance fluids is a thixotropic active substance fluid. In particular, however, all active ingredient fluids used should be thixotropic, preferably with approximately the same thixotropy. In this respect, reference may be made to the above-mentioned R ⁇ MPP literature reference for the explanation of the complex relationships of thixotropic active agent fluids.
• outlets 3, 4 show the receptacles 1, 2 with the outlets 3,4.
• the outlets 3, 4 are aligned parallel to one another.
• the flows of the active substance fluids can also be pre-aligned by already aligning the outlets 3, 4 of the receptacles 1, 2 somewhat towards one another. In terms of production technology, however, the parallel alignment shown has advantages.
• the blow molding method specifically implemented here it is possible, but not with the blow molding method specifically implemented here, to integrally form the ejection nozzle 6; 7 at the outlet 3; 4 on the receiving container 1; 2.
• this variant was not chosen in the exemplary embodiment shown. Rather, in the exemplary embodiment shown it is provided that the ejection nozzle se 6; 7 in a separate, here made of a dimensionally stable plastic nozzle head 12 is arranged or molded and that the nozzle head 12 is placed at the outlet 3; 4 on the receiving container 1; 2.
• the nozzle head 12 is identified in the figures by reference number 12. In the exemplary embodiment shown, the nozzle head 12 is snapped onto the receptacle 1; 2.
• The. Nozzle head 12 can also be connected to the receptacle 1; 2 in another way. However, snapping on is recommended as a particularly simple and expedient manufacturing technique.
• the illustrated and preferred exemplary embodiments are particularly distinguished by the fact that the nozzle heads 12 of the two receptacles 1, 2 are combined in a common nozzle head 12.
• This common nozzle head 12 can be seen in FIGS. 7, 8, 9 and 10 and 12, 14. This is very practical in terms of production technology and is optimally adapted to the connection of the two receptacles 1, 2.
• the nozzle head 12 can be seen in the figures given above and in FIGS. 5 and 6. In section, the nozzle head 12 can be seen particularly well in FIGS. 8, 9, 10. It can be seen that it is essential for the flow of the active substance fluid in FIG Nozzle head 12 is expedient for the ejection nozzle 6; 7 to be arranged asymmetrically in the nozzle head 12, in particular offset with respect to the center line of the outlet 3; 4 in the direction of the further ejection nozzles 7; 6. This can be seen particularly well in FIG. 8. The flow of the active substance fluid from the respective receiving container 1; 2 is brought to the desired distance from the active substance fluid flowing out in parallel.
• the nozzle head 12 has an inflow volume 13 tapering from the outlet 3; 4 of the receiving container 1; 2 to the ejection nozzle 6; 7.
• This inflow volume 13 can be understood particularly well in FIGS. 8 and 9.
• the illustrated and preferred exemplary embodiment shows a dimensioning such that the lateral center distance of the ejection nozzles 6; 7 on the outside is approximately 5 mm to approximately 30 mm, preferably approximately 15 mm to approximately 20 mm.
• the ejection nozzle 6; 7 can be closed with a removable closure cap 14, which preferably consists of a dimensionally stable plastic , It is provided that the closure cap 14 fits into the ejection nozzle 6; 7 entering sealing plug 15. This technique has already been tried and tested to avoid cross-contamination (see WO 91/04923 A1 above).
• the closure cap 14 has, in addition to the closure plug 15 entering the ejection nozzle 6; 7, a cylinder section 19 convexly curved to the longitudinal axis of the closure cap 14 as a positioning aid.
• This cylinder section 19 is spaced apart from the sealing plug 15 such that the free ends of the cylinder section 19 abut the ejection nozzles 6, 7 in the closed position.
• the lower ends of the cylinder sections 19 slide along the inclined surfaces of the ejection nozzles 6, 7, so that the movement is positively guided.
• the placement process of the closure cap 14 with the cylinder sections 19 as positioning aids and the closure plug 15 on the ejection nozzles 6, 7 is shown schematically in FIG. 14.
• FIGS. 1a, 1b and 14 show that it also applies to the closure cap 14 that it is combined for both ejection nozzles 6, 7 of the two receptacles 1, 2.
• This is expedient in terms of manufacturing technology, just as has already been explained as expedient in the case of the nozzle head 12.
• the closure cap 14 expediently consists of a similar or the same plastic material as the nozzle head 12.
• the ejection nozzles 6, 7 - of course - have a nozzle channel 16 or 17. It could be provided that the nozzle channels 16, 17 of the ejection nozzles 6, 7 are inclined towards one another. Then the emerging streams of Active substance fluids are already aligned to a common application field 5. However, the exemplary embodiment shown and so far preferred shows that the nozzle channels 16, 17 of the ejection nozzles 6, 7 are aligned parallel to one another. A slight inclination within the scope of, for example, the manufacturing tolerances is of course acceptable.
• the nozzle channels 16, 17 aligned parallel to one another, it is particularly expedient if the nozzle channels 16; 17 of the ejection nozzles 6; 7 each have a cross-sectional constriction 18 arranged asymmetrically to the overall flow cross section.
• the cross-sectional constriction 18 in the respective nozzle channel 16, 17 results in a certain swirl being imparted to the flows of the active substance fluids, so that a certain deflection takes place in the outlet area of the ejection nozzles 6, 7, so that the flows of the active substance fluids are then in the application field, at a distance that depends in some way on the pressure of the operator's hand on the receptacles 1, 2.
• the flows of the active substance fluids are therefore not brought together by aligning the nozzle channels 16, 17, but by influencing the flow.
• a complete coverage of the flows of the active substance fluids in the application field 5 and not only is achieved ei ⁇ e partial coverage achieved by scattering effect as it could occur with unmodified nozzle channels 16, 17.
• 11a, 11b shows the functional principle of the cross-sectional constrictions 18 at the top, an example of the arrangement of the cross-sectional constrictions 18 in the adjacent nozzle channels 16, 17 below.
• the cross-sectional constrictions 18 of the nozzle channels 16, 17 are designed with angular transitions. In terms of flow technology, this has the consequence that different flow velocities occur across the flow cross section of the nozzle channel 16; 17. Away from the cross-sectional constriction 18, the active substance fluid can flow comparatively undisturbed, it maintains a high flow velocity with a laminar flow.
• the embodiment according to 11b shows an inclined opening plane of the nozzle channels 16, 17, cf. also nozzle head 12 according to FIG. 12.
• the swirl effect due to different flow velocities is also generated in the outlet by the beveling of the ends of the eye channels.
• the swirl effect is caused by the fact that the openings of the nozzle channels of the ejection nozzles are bevelled against one another.
• the opening planes of the nozzle channels 6, 7 are arranged at an angle to one another, the section of the wall of the ejection nozzle which is on the inside relative to the longitudinal axis of the nozzle channel being longer than the section of the wall which is on the outside of the longitudinal axis of the nozzle channel.
• only slanted openings are provided at the end of the nozzle channel to produce the swirl effect, but not a cross-sectional constriction in the nozzle channel.
• the respective cross-sectional constriction 18 is designed as an arch that is curved inwards.
• 12a and 12b show further expedient cross-sectional configurations.
• different cross-sectional shapes for the cross-sectional constrictions 18 as well as for the nozzle channels 16, 17 may also be selected with the different active substance fluids.
• the length of the cross-sectional constriction 18 of the nozzle channel 16; 17 is only part of the length of the nozzle channel 16; 17 as a whole. It is particularly recommended that the aspect ratio be approximately 1: 2 to 1: 4, preferably approximately 1: 2.5 to 1: 3.
• the total length of the nozzle channel 16; 17 is approximately 2 mm to approximately 6 mm, preferably approximately 3 mm to approximately 5 mm, in particular is about 4 mm.
• the diameter of the nozzle channel 16; 17 is approximately 1.0 mm to approximately 4.0 mm, preferably approximately 1.5 mm to approximately 3.5 mm, in particular approximately 2.0 mm to approximately 2.5 mm ,
• active substance fluids which are applied with the dispenser bottle according to the invention depend primarily on the area of application. For example, for the purposes of disinfection (e.g. for toilet cleaning), different combinations of active fluids are used than in the area of detergents, dishwashing detergents or anti-corrosion agents.
• Claims 39 to 51 describe, according to the invention, particularly preferred combinations of active substance fluids as are used for different areas of application.
• these different combinations of active substance fluids are only to be understood as examples and in no way limit the scope of the dispenser bottle according to the invention to the combinations mentioned there.
• the dispenser bottle can contain, for example, formulations in the receptacles 1, 2 include, as described in DE 102 15 602 A1 and DE 101 49 719 A1, the entire content of which is hereby incorporated by reference.
• the teaching of the present invention also relates to various uses of a dispenser bottle, for which reference may be made to claim 54. Special application examples on the basis of which the invention can be traced again in individual applications, follow here. These do not limit the teaching of the present invention.
• Example 1 specifies various formulations of active substance fluids which can be used in a dispenser bottle according to the invention for toilet cleaning.
• Liquid toilet cleaners are well known in the market. Products of this type generally contain inorganic or organic acids to remove limescale and rust deposits, as well as surfactants to support cleaning, abrasives, viscosity regulators, antibacterial additives, colorants and perfumes to remove odors.
• alkaline toilet cleaners are known, which are formulated on the basis of sodium hypochlorite, surfactants and the above-mentioned additional components. These products have a good bleaching and disinfecting effect, but are not able to remove calcareous soiling.
• toilet cleaners All traditionally known toilet cleaners have in common that they are offered in monotank plastic bottles with special dosing attachments the.
• the formulation of a toilet cleaner in a monotank bottle requires that the active ingredients used are compatible with one another and have sufficient storage stability over a long period of time. This leads to restrictions in the formulation of effective cleaners, since the active ingredients usually used - acid, bleach, perfume oil, and abrasives - can enter into undesirable reactions, at least after a longer contact time.
• the dispenser bottle according to the invention enables the range of services of toilet cleaners to be expanded through the use of incompatible or reactive active ingredients.
• acidic peroxide-containing cleaning agents are extremely effective, both in their bleaching and disinfecting effects and in removing limescale deposits, but have only a low shelf life in conventional bottles.
• a cleaning agent that is stable over a considerably longer time is obtained.
• Another example is the combination of an alkaline, hypochlorite-containing bleaching agent in one chamber with an acidic and therefore descaling agent in the second chamber.
• the combination of an acidic agent with a carbonate-containing alkaline phase can only be achieved in a dispenser bottle according to the invention. When these two phases are mixed (when using the agent), carbon dioxide is released, which causes the agent to foam and supports cleaning performance.
• the agents described with decalcifying phase all show good lime dissolving activity, with values according to the IKW standard test of 150 to 350 mg calcium carbonate for the 1: 1 mixture of the two phases.
• the following formulation examples are by no means to be understood as a final list. Rather, all active ingredients known to the person skilled in the art can be used as constituents of cleaning agents in dispenser bottles according to the invention, so that meaningful combinations can be formulated within one phase. In particular, the stated amounts are not binding, but the above and other ingredients can be used within wide limits.
• Receptacle A Product with a highly acidic, perfume-free descaling phase
• Container B High quality fragrance phase
• Container A Descaling phase
• Acid e.g. Sulfamic acid 5.00 to 12.00% by weight
• Stabilizer e.g. Urea 2.00 to 6.50% by weight
• Nonionic surfactant eg fatty alcohol etho 0.50 to 5.00% by weight xylate C 13 8EO
• Dye e.g. Hostafine Blue B 2 G C.I. ⁇ 0.01% by weight
• Acid-stable thickener e.g. Xanthan (poly 0.01 to 2.00% by weight saccharide)
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle
• Receptacle B fragrance phase
• Nonionic surfactant e.g. alkyl (C 8 -C 10 ) - 0.50 to 5.00% by weight
• Thickeners e.g. Xanthan (polysaccharide) 0.01 to 2.00% by weight
• Perfume e.g. Luminous lemon (Dragoco) 0.10 to 1.00% by weight of dye, e.g. Lumogen Yellow (BASF; C.I. ⁇ 0.03% by weight Pigment Yello 101) tap water ad 100% by weight
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT,
• This formulation cannot be implemented in a single-chamber bottle, since high-quality perfumes are not sufficiently stable in storage due to the influence of acid. However, this is desirable because, in addition to optimal lime removal, a long-lasting fragrance is desired.
• Receptacle A Product with a highly acidic, fragrance-free descaling phase
• Receptacle B Highly perfumed, stabilized abrasive phase
• Container A Descaling phase
• Acid e.g. Sulfamic acid 5.00 to 12.00% by weight
• Stabilizer e.g. Urea 2.00 to 6.50% by weight
• Nonionic surfactant e.g. fatty alcohol etho 0.10 to 5.00% by weight xylate C 13 8EO
• Dye e.g. Hostafine Blue B 2 G C.I. ⁇ 0.01% by weight
• Acid-stable thickener e.g. Xanthan (poly 0.01 to 2.00% by weight saccharide)
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle
• Receptacle B fragrance phase with abrasive
• Nonionic surfactant e.g. alkyl (C 8 -C 10 ) - 0.50 to 5.00% by weight
• Polysaccharide e.g. Xanthan 0.01 to 2.00% by weight
• Perfume e.g. Outdoors (from Dragoco) 0.10 to 1.00% by weight
• Dye e.g. Lumogen Yellow (BASF; C.I. ⁇ 0.03%
• Abrasive e.g. aluminum oxide ⁇ 0.1 ⁇ m 0.50 to 2.0% by weight
• Preservatives e.g. Semi-acetal iso ⁇ 0.50% thiazoline combination
• the stability of high-quality fragrances and abrasives can be optimally achieved in an alkaline medium.
• the combination of strongly acidic decalcifier with a fragrance and abrasive phase leads to increased performance and gloss on the toilet ceramic when used mechanically with the toilet brush.
• Receptacle A Powerful descaler based on organic acids
• Receptacle B Reduces acidic abrasive formula with fragrance phase
• Container A Descaling phase with organic acids
• Acid e.g. Formic acid, citric acid, 5.00 to 12.00% by weight
• Nonionic surfactant e.g. alkyl (C 8 -C 10 ) - 0.10 to 6.00% by weight
• Dye e.g. Hostafine Blue B 2 G C.I. ⁇ 0.01% by weight
• Polysaccharide e.g. Xanthan 0.01 to 2.00% by weight
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle 31, at 20 n / min pH (conc.) 0.5 to 2.5
• Receptacle B Reduces acidic abrasive formula with fragrance phase
• Nonionic surfactant e.g. alkyl (C 8 -C 10 ) - 0.50 to 5.00% by weight 1,5-glucoside
• Acid e.g. formic acid, citric acid, 1.5 to 6% by weight mixtures
• Polysaccharide e.g. Xanthan 0.01 to 2.00% by weight
• Dye e.g. Lumogen Yellow (BASF; C.I. ⁇ 0.03% by weight Pigment Yellow 101)
• Abrasive e.g. aluminum oxide ⁇ 0.1 ⁇ m 0.50 to 5.00% by weight preservative, e.g. semi-acetal iso-0.10% thiazoline combination Tap water ad 100%
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle
• the perfume is selected in such a way that sufficient stability is guaranteed in the reduced fragrance / abrasive phase.
• the maximum cleaning effectiveness is achieved by the reinforcement with the descaling phase (more acidic).
• Receptacle A Product with a highly acidic, fragrance-free descaling phase
• Receptacle B High quality perfumed reactive-foaming abrasive phase
• Container A Descaling phase
• Acid e.g. Sulfamic acid 5.00 to 12.00% by weight
• Stabilizer e.g. Urea 2.00 to 6.50% by weight
• Nonionic surfactant for example fatty alcohol etho 0.10 to 6.00% by weight xylate C 13 8EO
• Dye e.g. Hostafine Blue B 2 G C.I. ⁇ 0.01% by weight
• Acid-stable thickener e.g. xanthan (poly 0.01 to 2.00 wt .-% saccharide) tap water ad 100% by weight
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle 31, at 20 n / min pH value (conc.) 0.5 to 2.5
• Receptacle B Highly perfumed, reactive foaming
• Anionic surfactant eg sec. C 14 . 17 alkane 0.50 to 5.00% by weight sulfonate-Na reactive abrasive, eg calcium carbonate 0.10 to 2.00% by weight • fine, powder of non-reactive abrasive, eg aluminum 1, 00 to 3, 00% by weight oxide ⁇ 0.1 ⁇ m
• Polysaccharide e.g. Xanthan 0.01 to 2.00% by weight
• Perfume e.g. Outdoors (Dragoco) 0.10 to 1.00% by weight
• Dye e.g. Sicovit quinoline yellow ⁇ 0.03%
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle
• Receptacle A White alkaline abrasive phase
• Receptacle B Colorless, neutral cleaner with indicator
• Receptacle A White alkaline abrasive phase
• Nonionic surfactants e.g. fatty alcohol etho 0.10 to 6.00% by weight xylate C 13 . 14 6EO, fatty alcohol C 12 - ⁇ 4 . 6.4 EO,
• Alkali e.g. Monoethanolamine 0.10 to 1.00% by weight
• Abrasive e.g. Calcium carbonate 15 mic 15 to 40 wt .-% ron
• Perfume e.g. Lemon (Dragoco) 0.10 to 1.0% by weight
• Thickeners e.g. Rohagit (acrylate) 0.01 to 2.00% by weight
• Viscosity 750 to 2000 mPas, 20 ° C Rotovisko LVT, spindle
• Receptacle B Colorless, neutral cleaner with indicator thickener, e.g. Xanthan (polysaccharide) 0.01 to 2.00% by weight
• Indicator e.g. Phenolphthalein (1.0%) 0.50 to 2.00% by weight
• Viscosity 350 to 800 mPas, 20 ° C Rotovisko LVT, spindle
• a color reaction occurs on the ceramic surface (for example, pink when using phenolphthalein as an indicator), which can only be achieved via the dispenser bottle according to the invention.
• suitable indicator dyes with specific pH ranges allows use in the neutral-alkaline or neutral-weakly acid range.
• Container A Product with an acidic, perfumed decalcifying phase
• Receptacle B Product with alkaline Na hypochlorite phase with bleaching and disinfecting effects
• Container A Product with an acidic, perfumed decalcifying phase
• Acid e.g. Sulfamic acid, citric acid, 7.00 to 18.00% by weight
• Nonionic surfactant for example fatty alcohol etho 0.10 to 5.00% by weight xylate C 13 8EO
• Alkali e.g. sodium hydroxide 0.10 to 2.00% by weight
• Acid-stable thickener e.g. Xanthan (poly 0.01 to 2.00% by weight saccharide)
• Dye e.g. Hostafine Green 6N ⁇ 0.01% by weight
• Acid-stable perfume e.g. B. Fontana (Fa. 0.10 to 1.00% by weight
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle 31, at 20 n / min pH (conc.) 0.5 to 3.0
• Receptacle B Product with alkaline NaHvpochloritphase with
• Anionic surfactant e.g. Na alkyl sulfate C 12 . 1.00 to 5.00% by weight
• Alkali e.g. Caustic soda 0.50 to 2.00% by weight
• Dye e.g. Hostafine Blue B 2 G C.I. ⁇ 0.01% by weight
• Thickeners e.g. Xanthan (polysaccharide) 0.01 to 2.00% by weight
• Viscosity 200 to 600 mPas, 20 ° C Rotovisko LVT, spindle
• Container A Product with an acidic, perfumed decalcifying phase
• Receptacle B Product with a stabilized hydrogen peroxide phase with bleaching and disinfecting effects
• Container A Product with an acidic, perfumed decalcifying phase
• Acids e.g. Citric acid, formic acid, 5.00 to 12.00% by weight
• Nonionic surfactant for example fatty alcohol etho 0.10 to 6.00% by weight xylate C 13 8EO
• Acid-stable thickener e.g. Xanthan (poly 0.01 to 2.00% by weight saccharide)
• Dye e.g. Hostafine Blue B 2 G C.I. ⁇ 0.01% by weight
• Acid-stable perfume 0.1 to 1.0% by weight
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle
• Receptacle B Product with a stabilized hydrogen peroxide phase with bleaching and disinfecting effects
• Nonionic surfactant eg fatty alcohol etho 0.10 to 6.00% by weight, xylate C 13 8EO
• Stabilizer radical scavenger, mixtures 0.05 to 6.00% by weight
• Dye e.g. Hostafine Blue B 2 G C.I. ⁇ 0.01% by weight
• Viscosity 500 to 1000 mPas, 20 ° C Rotovisko LVT, spindle
• Example 2 specifies various formulations of active substance fluids which can be used in a dispenser bottle according to the invention for manual or machine dishwashing.
• the dispenser bottle according to the invention not only makes it possible to increase the storage stability of flowable substances or substance mixtures, in particular machine or manual dishwashing detergents, but by using separate receptacles, the stability of the active substances contained in the detergents can be improved and at the same time made possible by separating chemically incompatible ingredients this procedure also the simple and inexpensive assembly of flowable substances in the form of "multiphase" offer forms.
• the interaction of different active substances in automatic dishwashing detergents can be visualized on the way of multi-phase or multi-phase.
• the volume of the storage containers depends, among other things, on the weight or volume fraction of these active substances in the overall formulation of the automatic dishwashing detergent or the way in which these active substances are packaged, for example in the form of the pure substance, as a solution or dispersion.
• all receptacles have the same size, their volume preferably being between 10 and 2000 ml, preferably between 20 and 1500 ml, particularly preferably between 50 and 1000 ml and in particular between 100 and 800 ml.
• Dispenser bottles according to the invention are suitable for repeated dosing of the flowable machine dishwashing detergents and accordingly contain at least two, but preferably at least 6, particularly preferably at least 12, 24 or 36 dosing units.
• the liquids contained in the packs according to the invention can be both water-containing and water-free formulations. There may also be separate water-containing and water-free formulations in one package.
• Commercial water-containing automatic dishwashing detergents have a water content of between 10 and 70% by weight, particularly preferably between 20 and 60% by weight and in particular between 30 and 50% by weight, in each case based on the total weight of the water-containing automatic dishwashing detergent
• preferred water-free automatic dishwashing detergents have a water content below 6% by weight, preferably between 0.5 and 5% by weight, particularly preferably between 1 and 4% by weight, in each case based on the total weight of the water-free machine dishwashing detergent.
• the liquid matrix of the aforementioned water-containing or water-free automatic dishwashing detergents can of course also contain other non-aqueous solvents in addition to the water.
• These non-aqueous solvents originate, for example, from the group of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides.
• Non-aqueous solvents which are water-soluble are particularly preferred, "water-soluble" solvents in the sense of the present application being solvents which are completely, ie. H. without a miscibility gap.
• Non-aqueous solvents which can be used in the dispenser bottles according to the invention preferably come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
• the solvents are preferably selected from ethanol, n-propanol or isopropanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethene lenglycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, eth
• Flowable substances and / or substance mixtures which are particularly preferred in the context of the present invention are characterized in that they particularly non-aqueous solvents in amounts of 0.1 to 70 wt .-%, preferably from 0.5 to 60 wt .-% preferably from 1 to 50% by weight, very particularly preferably from 2 to 40% by weight and in particular from 2.5 to 30% by weight, in each case based on the solvent-containing flowable substance or the flowable substance mixture, preferred ⁇ ) non-aqueous solvent (s) is / are selected from the group of the nonionic surfactants which are liquid at room temperature, the polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso propanol.
• preferred ⁇ ) non-aqueous solvent (s) is / are selected from the
• flowable solids such as, for example, powders, granules or microcompacts, also apply as flowable substances / substance mixtures in the context of the present application.
• the solids mentioned can be in amorphous and / or crystalline and / or partially crystalline form.
• the particle size of these flowable solids is preferably in the range from 10 to 2000 ⁇ m, particularly preferably in the range from 20 to 1000 ⁇ m and in particular in the range from 50 to 500 ⁇ m.
• Flowable solids in which at least 70% by weight of the particles, preferably at least 90% by weight of the particles, have a particle size below 1000 ⁇ m are particularly preferred. preferably below 800 ⁇ m, particularly preferably below 400 ⁇ m.
• further active substances can preferably be selected from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH regulators, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, anti-redeposition agents, antimicrobial agents, germicides, fungicides, antioxidants and corrosion inhibitors can be included.
• the dispenser bottle according to the invention is particularly suitable for separating ingredients from cleaning agents which are incompatible with one another.
• the following table shows a non-exhaustive list of the separation of incompatible ingredients in multi-chamber bottles with two storage containers.
• Example 2 gives various formulations of active substance fluids which can be used in a dispenser bottle according to the invention, hereinafter also referred to as a multi-chamber container, for the manual or machine washing of textiles.
• Example 3 shows that, surprisingly, it was found that from the point of view of the storage stability and the performance of the detergent under application conditions, an optimum results when using a liquid detergent composition which consists of at least two separate water-containing partial compositions, a first partial composition contains organic peracid and contains a second sub-composition of surfactant and enzyme.
• the separation of the partial compositions is preferably carried out by the fact that they are present in the dispenser bottle according to the invention as a multi-chamber container, the number of chambers (receiving containers) of the container corresponding to the number of partial compositions and only one of the partial compositions being present in each of the chambers.
• Another object of the invention is therefore a combination of a liquid detergent composition defined here, which consists of at least two, preferably exactly two sub-compositions as active fluids, and a dispenser bottle, the number of chambers of the container corresponding to the number of sub-compositions and in each case one of the chambers, one of the partial compositions is present.
• the chambers are either designed separately and connected to one another or made in one piece with one another.
• Each of the chambers has at least one, preferably exactly one, outlet in the form of an outlet nozzle from which the partial composition can emerge from the respective chamber. This can be done by gravity, ie tilting the dispenser bottle so that the partial composition of the liquid detergent composition flows out.
• the dispenser bottle can be squeezed so that the outflow of the components can be accelerated by pressure on the dispenser bottle, for example, by the hand of an operator.
• the outlet of a liquid detergent container is usually provided with a closure cap, in the case of the present invention the outlet of each chamber can be provided with its own closure cap or the closure cap can be designed such that it closes several, in particular all, outlets of the dispenser bottle.
• the dispenser bottle can have grips or handles, the handle being attached to one or more chambers, or can also be part of a chamber, or several chambers each form a handle and they are joined together in such a way that the Dispenser bottle or the multi-chamber container can be gripped by the user's hand.
• the separate storage in the dispenser bottle or the multi-chamber container means that the partial compositions of the liquid detergent composition only mix with one another after they have left the outlets, for example when pouring into a conventional washing-up chamber of a washing machine or into a washing drum of such a washing machine Washing machine with dosing device to be introduced, or when spraying the agent onto a textile surface in need of cleaning, for example as part of the pretreatment of laundry.
• the chambers of the multi-chamber container each have at least one, preferably exactly one ejection nozzle, and that the nozzle channels the ejection nozzles are aligned essentially parallel to one another, but each have a cross-sectional constriction arranged asymmetrically to the overall flow cross-section.
• the cross-sectional constrictions are preferably arranged on the mutually facing sides of the nozzle channels in such a way that the partial compositions emerging under pressure have a swirl directed towards one another.
• the dispenser bottle can consist of a material with a resetting characteristic and / or can have a shape that supports the resetting into the original shape. In particular, it is advisable to manufacture the dispenser bottle from an elastically resilient plastic material.
• the material for the bottle body or the multi-chamber container is, for example, a polyolefin, in particular polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC) or polyethylene terephthalate (PET), in particular glycol-modified polyethylene terephthalate (PETG), act.
• a polyolefin in particular polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC) or polyethylene terephthalate (PET), in particular glycol-modified polyethylene terephthalate (PETG), act.
• the material can also be of one or more colors, the individual chambers of the multi-chamber container being able to have the same color or the same colors or different colors from one another.
• Multi-chamber containers are known, for example, from international patent applications WO 02/22467 A1, WO 97/23087 A1, WO 96/12648 A1, WO 95/16023 A1, WO 91/04923, German patent application DE 32 20 693 A1 or German utility model DE G 93 16583 U1 known.
• the liquid detergent composition according to the invention contains no bleach activator.
• the first partial composition as the first active substance fluid preferably consists essentially of water and the organic peracid, which can be dissolved in water, but particularly preferably is at least partially undissolved in finely divided form.
• the first partial composition may also contain the organic acid corresponding to the organic peracid and small amounts of conventional stabilizers for bleaching agents, for example the vinyl ether-maleic acid copolymers known from European patent application EP 1 074 607 as dispersants and / or those from European Patent EP 0 497 337 known nonionic surfactants and / or complexing agents which counteract the metal-catalyzed decomposition of the peracid.
• the content of organic peracid is preferably 1% by weight to 25% by weight, in particular 2% by weight to 20% by weight and particularly preferably 3% to 15% by weight, in each case based on the first partial composition.
• the organic peracid can carry aliphatic and / or cyclic, including heteroeyclic and / or aromatic, residues.
• peroxoformic acid peroxoacetic acid, peroxopropionic acid, peroxohexanoic acid, peroxobenzoic acid and their substituted derivatives such as m-chloroperoxobenzoic acid, the mono- or di-peroxophthalic acids, 1, 12-diperoxododecanedioic acid, nonylamidoperoxo-adipoic acid, 6-hydroxy-peroxanoic acid, 6-hydroxyoxyacid, 6-hydroxyoxyacid, 6-hydroxyoxyacid, 6-hydroxyoxyacid, 6-hydroxyoxyacid , 5-phthalimidoperoxopentanoic acid, 6-
• the first partial composition preferably has an acidic pH, in particular in the range from pH 1.5 to pH 5 and particularly preferably from pH 2.5 to pH 4.5, which results from the presence of the organic peracid or from the addition system - compatible acids can be adjusted.
• the first sub-composition does not contain hydrogen peroxide.
• the first partial composition in one embodiment of the invention can contain anionic surfactant compatible with the organic peracid in amounts of up to 50% by weight, in particular 10% by weight to 30% by weight, in each case based on the first partial composition.
• the second partial composition as the second active fluid or each of the further partial compositions optionally contains at least one enzyme in addition to surfactant and is free from oxidative bleaching agents.
• Mixtures of nonionic and anionic surfactant are particularly preferred, the second partial composition or each of the optionally further partial compositions may contain a mixture of nonionic and anionic surfactant or at least the second partial composition may contain nonionic surfactant and at least one further partial composition anionic surfactant.
• Enzyme mixtures can likewise be contained in the sub-compositions, or a plurality of enzymes can be distributed over the second and the further sub-compositions in such a way that each of them contains only one enzyme.
• the second or at least one of the further partial compositions can be alkaline, so that after pouring out of the multi-chamber container, that is to say when all the partial ingredients have been combined.
• compositions a preparation results which has a pH of preferably 4.5 to 10, in particular 5 to 9.
• the second partial composition preferably contains 8% by weight to 70% by weight, in particular 20% by weight to 55% by weight, of water.
• the surfactants contained in the second partial composition or the further partial compositions include, in particular, anionic surfactants and nonionic surfactants, although cationic surfactants and amphoteric surfactants can also be considered.
• Anionic surfactants used are preferably one or more substances from the group of carboxylic acids, sulfuric acid half-esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids.
• the compounds mentioned should have longer-chain hydrocarbon radicals, that is to say they should have at least 6 carbon atoms in the alkyl or alkenyl radical.
• the C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.
• Carboxylic acids which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage.
• Carboxylic acids which can be used as anionic surfactants in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), hep- tanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc.
• fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid is preferred in the context of the present compound.
• canoic acid canoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid) as well as the unsaturated acidic acid 9c-hexadecenoic acid-6c-hexadecenoic acid (Petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linosilicateic acid) and 9
• Such mixtures are, for example, cos oil fatty acid (approx. 6% by weight C8, 6% by weight C10, 48% by weight C12, 18% by weight C14, 10% by weight C16, 2% by weight C18, 8% by weight C18 ' , 1% by weight C18 " ), palm kernel oil fatty acid (approx. 4% by weight C8, 5% by weight C10, 50% by weight C12, 15% by weight C14 , 7% by weight C16, 2% by weight C18, 15% by weight C18 ' , 1% by weight C18 "), tallow fatty acid (approx.
• Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants and can be used in the context of the present invention.
• Your alkali metal, especially sodium salts, the so-called fatty alcohol sulfates are commercially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the relevant alkyl sulfuric acids and subsequently neutralized.
• the fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters.
• the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with S03 / air mixtures in special cascade, falling film or tube bundle reactors.
• alkyl ether sulfuric acids the salts of which, the so-called alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
• alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question.
• ethylene oxide propylene oxide can also be used.
• the subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the alkyl ether sulfuric acids concerned.
• Alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention.
• Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the C chain (secondary alkanes sulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are produced by sulfochlorination or sulfoxidation of linear hydrocarbons.
• n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which give the alkanesulfonates directly when hydrolysed with alkalis, and the alkanesulfonic acids when reacted with water.
• di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.
• alkanesulfonic acids Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under irradiation with UV light.
• This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals.
• the reaction with unreacted paraffin gives an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical.
• the reaction of the two radicals with unreacted paraffin gives the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to give sulfuric acid.
• this reaction is usually carried out only up to degrees of conversion of 1% and then stopped.
• Olefin sulfonates are produced industrially by the reaction of ⁇ -olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize to form so-called sultons. Under suitable conditions conditions (alkaline or acidic hydrolysis) these sultones react to give hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids.
• alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
• propylene was tetramerized to give branched ⁇ -dodecylene and the product was converted to a tetrapropylenebenzene using a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized.
• TPS tetrapropylene benzene sulfonates
• Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins.
• petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrated to the n-olefins, resulting in both ⁇ - and i-olefins.
• C8-16-, preferably C9-13-alkylbenzenesulfonic acids are preferred as anionic surfactants according to the invention in acid form.
• alkylbenzenesulfonic acids which are derived from alkylbenzenes and which have a tetralin content below 5% by weight, based on the alkylbenzene.
• alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C8-16-, preferably C9-13-alkylbenzenesulfonic acids used have a 2-phenyl isomer content of less than 22% by weight on the alkylbenzenesulfonic acid.
• the anionic surfactants mentioned can be used alone or in a mixture with one another, mixtures of fatty acids and ether sulfates, in particular in weight ratios of 5: 1 to 1: 5, preferably 2: 1 to 1: 2, being particularly preferred.
• the anionic surfactants described above in their acid form are usually used in partially or fully neutralized form.
• ammonium and mono-, di- or triethanolammonium ions are suitable as cations for the anionic surfactants.
• the analog representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• the preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C9-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used.
• Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• Low-foaming nonionic surfactants can also be used which have alternating ethylene oxide and alkyl oxide units.
• surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Examples of these are surfactants of the general formula
• R1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical; each group R2 or R3 is independently selected from -CH3; - CH2CH3, -CH2CH2-CH3, CH (CH3) 2 and the indices w, x, y, z independently of one another represent integers from 1 to 6.
• R1-OH a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical
• each group R2 or R3 is independently selected from -CH3; - CH2CH3, -CH2CH2-CH3, CH (CH3) 2 and the indices w, x, y, z independently of one another represent integers from 1 to 6.
• the residue R1 has an even number of carbon atoms and is usually not shown, the linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat. or omelial alcohol are preferred.
• Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues.
• compositions according to the invention are preferred in which R1 in the above formula for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
• R1 in the above formula for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
• butylene oxide in particular can be used as the alkylene oxide unit, which can be contained in the nonionic surfactants alternately with the ethylene oxide unit.
• R2 or R3 are selected independently of one another from -CH2CH2-CH3 or CH (CH3) 2 are also suitable.
• nonionic surfactants can also be alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms means and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
• nonionic surfactants used either as the sole nonionic surfactant or in combination with other whose nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
• Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula below.
• RCO for an aliphatic acyl radical with 6 to 22 carbon atoms
• R1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 Hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula R 1 -OR
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
• R2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C1-4-alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• R1 and R2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
• x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R3 in the above formula can be different.
• R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 6 to 22 carbon atoms, radicals with 8 to 18 carbon atoms being particularly preferred.
• H, -CH3 or -CH2CH3 are particularly preferred for the radical R3. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
• alkoxylated fatty alcohols and alkyl glycosides are preferred among the nonionic surfactants.
• the weight ratio of which is preferably 10: 1 to 1: 2, in particular 10: 1 to 2: 1.
• the weight ratio of anionic surfactant to nonionic surfactant is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. It is preferred if the surfactant is present in amounts of from 5% by weight to 80% by weight, preferably from 7.5% by weight to 70% by weight, particularly preferably from 10% by weight to 60% by weight and in particular from 12.5% by weight to 50% by weight.
• the amounts and ratios given relate in one embodiment of the invention to the individual (second or further) partial compositions and in a further embodiment to the entire agent according to the invention.
• the enzymes contained in the second partial composition or the further partial compositions include in particular protease, amylase, lipase, hemicellulase and / or cellulase. In principle, these enzymes are of natural origin; based on the natural molecules are used in detergents and cleaning agents improved variants are available, which are used accordingly preferentially.
• Agents according to the invention contain enzymes in the second partial composition or the further partial compositions preferably in total amounts of 1 ⁇ 10-6 to 5 percent by weight, based on active protein.
• the protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 (1948), pp. 751-766).
• the first partial composition is free of enzymes.
• the second partial composition contains protease, amylase and cellulose. In this case, further partial compositions (ie apart from the first one) may be completely absent.
• subtilisin type those of the subtilisin type are preferred.
• subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K, which can no longer be assigned to the subtilisins in the narrower sense and the proteases TW3 and TW7.
• Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvasrd, Denmark.
• the subtilisins 147 and 309 are marketed by Novozymes under the trade names Esperase® and Savinase®, respectively.
• the protease from Bacillus lentus DSM 5483 (known from the international patent application WO 91/02792) is derived from the variants listed under the name BLAP®, which are found in particular in the international patent applications WO 92/21760, WO 95/23221 and in the German ones Patent applications DE 101 21 463 and DE 101 53 792 are described. More reversible proteases from various Bacillus sp. and B. gibsonii emerge from German patent applications DE 101 62 727, DE 101 63 883, DE 101 63 884 and DE 101 62 728.
• proteases are, for example, those under the trade names Durazym®, Relase®, Everläse®, Nafizym®, Natalase®, Kannase® and Ovozymes® from Novozymes, those under the trade names Purafect®, Purafect® OxP and Properase® from Genencor, which under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P® from from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
• amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments which are improved for use in detergents and cleaning agents.
• the enzyme from B. licheniformis is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar®ST. Further development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl® and Termamyl®ultra, from Genencor under the name Purastar®OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
• the ⁇ -amylase from B. amyloliquefaciens is sold by Novozymes under the name BAN®, and derived variants from the ⁇ -amylase from B. stearothermophilus under the names BSG® and Novamyl®, also from Novozymes. Furthermore, those in the international Patent application WO 02/10356 disclosed ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B.
• DSM 12368 DSM 12368
• CTTase cyclodextrin glucanotransferase
• agaradherens (DSM 9948) described in the international patent application PCT / EP01 / 13278; furthermore those which belong to the sequence space of ⁇ -amylases, which is defined in German patent application DE 101 31 441 A1. Fusion products of the molecules mentioned can also be used, for example those known from German patent application DE 101 38753.
• the further developments of the ⁇ -amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from Novozymes are suitable.
• Another commercial product is the Amylase-LT®.
• Agents according to the invention can contain lipases and / or cutinases. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®.
• the cutinases which were originally isolated from Fusarium solani pisi and Humicola insolens, can also be used.
• lipases are available from Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillis sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML® available.
• the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
• Agents according to the invention can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
• These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-redeposition effect or graying inhibition) and finish (tissue effect), through to the exertion of a "stone washed" effect.
• a usable fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme®.
• Endolase® and Carezyme® which are also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800. Other commercial products from this company are Cellusoft® and Renozyme®.
• the cellulases disclosed in international patent application WO 97/14804 can also be used; for example the 20 kD EG from Melanocarpus disclosed therein, which is available from AB Enzymes, Finland, under the trade names Ecostone® ) and Biotouch®.
• Other commercial products from AB Enzymes are Econase® and Ecopulp®.
• CBS 670.93 and CBS 669.93 are disclosed in the international patent application WO 96/34092, wherein the from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax®. Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge®Neutra. Agents according to the invention can contain further enzymes, which are summarized under the term hemicellulases.
• Suitable mannanases are available, for example, under the names Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec® B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
• a suitable ⁇ -glucanase from a B. alcalophilus can be found, for example, in the international patent application WO 99/06573.
• the ⁇ -glucanase obtained from B. subtilis is available under the name Cereflo® from Novozymes.
• the enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
• Agents according to the invention can contain enzyme stabilizers for this purpose.
• a group of enzyme stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example according to the international patent application O 95/12655 ortho-substituted, according to the international patent application WO 92/19707 meta-substituted and according to the US Pat. No.
• Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C12, for example from European patent application EP 0 378 261 or international patent application WO 97/05227, such as succinic acid, other dicarboxylic acids or salts of the acids mentioned.
• end group-capped fatty acid amide alkoxylates are disclosed for this purpose.
• Certain organic acids used as builders as disclosed in international patent application WO 97/18287, can additionally stabilize an enzyme contained.
• Lower aliphatic alcohols such as ethanol or propanol, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are further useful enzyme stabilizers.
• di-glycerol phosphate also protects against denaturation by physical influences.
• Calcium salts are also frequently used, such as calcium acetate or the calcium formate disclosed for this purpose in European patent EP 0 028 865, and magnesium salts, for example according to European patent application EP 0 378 262. Reducing agents and antioxidants increase, as disclosed inter alia in European patent application EP 0 780 466, the stability of enzymes against oxidative decomposition.
• Sulfur-containing reducing agents are known, for example, from European patents EP 0 080 748 and EP 0 080 223. Other examples of this are sodium sulfite (according to European patent application EP 0 533 239) and reducing sugars (according to European patent application EP 0 656 058).
• Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax according to international patent application WO 96/31589, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids according to European patent application EP 0 126 505 or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts, as disclosed in European patent application EP 0 080 223.
• peptide-aldehyde stabilizers is increased according to international patent application WO 98/13462 by the combination with boric acid and / or boric acid derivatives and polyols and according to international patent application WO 98/13459 by the additional use of divalent cations, such as Example calcium ions further enhanced.
• the second sub-composition or the further sub-compositions can moreover have all the ingredients customary in liquid detergents which do not interact negatively with the abovementioned ones.
• these include, for example, building materials, complexing agents for heavy metals, non-aqueous water-miscible solvents, thickeners, graying inhibitors, foam regulators, color transfer inhibitors, antimicrobial active ingredients. fabrics, optical brighteners, dyes and fragrances.
• such further ingredients can also be contained in the first partial composition, provided that they do not unreasonably impair the storage stability of the peracid component.
• silicates As builder materials which can be contained in the agents according to the invention, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are to be mentioned in particular.
• Suitable crystalline, layered sodium silicates have the general formula NaMSix02x + 1.
• y H20 where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4.
• M sodium or hydrogen
• x is a number from 1, 9 to 4
• y is a number from 0 to 20 and are preferred values for x 2, 3 or 4.
• Such crystalline layered silicates are described, for example, in European patent application EP 0 164514.
• Preferred crystalline layered silicates of the formula given are those in which M stands for sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate Na2Si205.yH20 are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
• Amorphous sodium silicates with a module Na20: Si02 of 1: 2 to 1: 3.3, preferably of 1: 2 to 1: 2.8 and in particular of 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used
• the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying.
• the term “amorphous” also means “X-ray amorphous ".
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can even lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in the case of electron diffraction experiments, which is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024.
• Compressed / compact are particularly preferred tated amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.
• the optionally used finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
• zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P are also suitable.
• Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa20. (1- n) K20. AI203. (2 - 2.5) Si02.
• the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture Come into play.
• the zeolite can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12-C18 fatty alcohols with 2 to 5 ethylene oxide groups, G12 - C14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method, for example using a Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
• the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
• Organic builder substances which can be used are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
• these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
• the acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to establish a lower one and milder pH of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
• the molar masses given for polymeric polycarboxylates in the sense of the present document are weight-average molar masses Mw of the respective acid form, which can in principle be determined by means of gel permeation chromatography (GPC), a UV detector being used.
• GPC gel permeation chromatography
• the measurement is carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated.
• This information differs significantly from the molecular weight data in which polystyrene sulfonic acids are used as standard, the molar masses measured against polystyrene sulfonic acids generally being significantly higher.
• Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol.
• the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid known from European patent EP 0 727 448 B1, as a monomer.
• biodegradable polymers composed of more than two different monomer units, for example those which, according to German patent application DE 43 00 772 A1, are monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to German patent DE 42 21 381 as monomers contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
• Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• Also to be mentioned as further preferred organic builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
• polyaspartic acids or their salts and derivatives are particularly preferred, of which it is disclosed in German patent application DE 195 40 086 A1 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
• Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223.
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out according to customary, for example acid or enzyme-catalyzed processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.
• a preferred dextrin is described in European patent application EP 0 703 292 A1.
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0 232 202, EP 0427 349, EP 0 472 042 and EP 0 542496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
• An oxidized oligosaccharide according to German patent application DE-A-19600 018 is also suitable.
• a product oxidized at C6 of the saccharide ring can be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable builder materials.
• Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts.
• EDDS Ethylene diamine N, N'-disuccinate
• glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
• glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in US Pat European patent application EP-A-0 150 930 and Japanese patent application JP 93/339896.
• Further usable organic builders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups.
• Such builders are described, for example, in international patent application WO 95/20029.
• Builder substances, and among these in particular water-soluble materials, are preferably present in the compositions according to the invention in amounts of 1% by weight to 20% by weight, in particular 1% by weight to 8% by weight, the first partial composition preferably being free of builder materials.
• the complexing agents for heavy metals which may be present in the compositions include phosphoric acid, aminocarboxylic acids and optionally functionally modified phosphonic acids, for example hydroxy- or aminoalkanephosphonic acids.
• the aminocarboxylic acids which can be used include, for example, nitrilotriacetic acid, methylglycinediacetic acid and diethylenetriaminepentaacetic acid.
• the phosphonic acids include, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or the disodium salt or the tetrasodium salt of this acid, 2-phosphonobutane-1, 2,4-tricarboxylic acid or the trisodium salt of this acid, ethylenediaminetetramethylenephosphonic acid (EDTMP) ), Diethylenetriamine-pentamethylenephosphonic acid (DTPMP) as well as their higher homologues in question.
• HEDP 1-hydroxyethane-1,1-diphosphonic acid
• ETMP ethylenediaminetetramethylenephosphonic acid
• DTPMP Diethylenetriamine-pentamethylenephosphonic acid
• the N-oxides corresponding to the nitrogen-containing compounds mentioned can also be used.
• the usable complexing agents also include ethylenediamine-N, N '- disuccinic acid (EDDS).
• complexing agents mentioned in their acid form can be used as such or in the form of their alkali metal salts, in particular the Sodium salts are used. Mixtures of aminocarboxylic acids with phosphonic acids are preferred.
• Complexing agents for heavy metals are preferably contained in the agents according to the invention in amounts of 0.05% by weight to 1% by weight, if desired they can be contained in the first partial composition and / or in the second or the further partial compositions.
• Non-aqueous solvents which can be used in the agents according to the invention come, for example, from the group of monohydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range intended for use.
• the solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybut
• non-aqueous solvents can be used in the liquid detergents according to the invention in amounts of up to 40% by weight, preferably from 0.5 to 20% by weight and in particular from 1% by weight to 10% by weight the abovementioned solvents include the amounts of those which also act as enzyme stabilizers at the same time.
• Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils. Silicone oils are preferably used.
• Suitable antiredeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight on the nonionic cellulose ether, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.
• Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances absorb onto the fiber and cause a whitening and fake bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and with the yellow tone of the grayed or yellowed laundry gives pure white.
• Suitable compounds originate from the substance classes of the 4,4 'diamino-2,2' - stilbenedisulfonic (flavonic), 4,4'-biphenylene -Distyryl, belliferone Methylum-, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides Acid imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.
• the optical brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished agent.
• Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
• Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
• cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, are preferably used
• the agents according to the invention can contain synthetic anti-crease agents, but these are preferred are not included in the first sub-composition. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
• the agents according to the invention can contain antimicrobial agents.
• antimicrobial agents A distinction is made here according to the antimicrobial spectrum and mechanism of action between bacteriostatics and bactericides, fungistatics and fungicides, etc.
• Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, whereby ⁇ these compounds can be dispensed with entirely in the agents according to the invention.
• Thickening agents that can be used in the partial compositions according to the invention are, for example, those from the class of polyurethanes, polyacrylates, which may also be at least partially crosslinked, polyacrylamides and / or polysaccharides or their derivatives.
• a polysaccharidic thickening active ingredient is an optionally modified polymer of saccharides such as glucose, guest lactose, mannose, gulose, old rose, allose, etc.
• a water-soluble xanthan such as is commercially available, for example, under the product names Kelzan®, Rhodopol®, Ketrol® or Rheozan® is preferably used.
• Xanthan is understood to be a polysaccharide which corresponds to that which is produced by the bacterial strain Xanthomonas campestris from aqueous solutions of glucose or starch (J. Biochem. Micobiol. Technol. Engineer. Vol. III (1961), pp. 51 to 63) , It consists essentially of glucose, mannose, glucuronic acid and their acetylene products and also contains minor amounts of chemically bound pyruvic acid.
• water-soluble polysaccharide derivatives such as, for example, by oxalkylation with, for example, ethylene oxide, propylene oxide and / or butylene oxide, by alkylation with, for example, methyl halides and / or dimethyl sulfate, by acylation with carboxylic acid halides or by saponifying deacetylation from the corresponding polysaccharides can be obtained is possible.
• Thickening agents are present in the agents according to the invention in amounts of preferably 0.05% by weight to 2.5% by weight, in particular 0.1% by weight to 2% by weight, the proportion of which is not the same in all the partial compositions must be large.
• the individual partial compositions are preferably used in equal proportions. This can be achieved in a simple manner by adjusting the viscosity of the partial compositions and / or the type of the outlet openings of the chambers of the multi-chamber container, in particular the adjustment of the diameter of the outlet openings, so that the user of the agent simply by pouring out or squeezing out the multi-chamber container easily usable amount, for example the amount necessary for a wash in a washing machine, liquid detergent.
• surfactant and enzyme-containing partial compositions T1 and T2 were prepared. These were each filled into a chamber of a double chamber bottle made of polyethylene consisting of two chambers of equal size (volume 750 ml each) and the second chamber of the bottle with the same amount of a 5% by weight aqueous phthalimidoperoxohexanoic acid preparation P (Eureco® L, manufacturer Ausimont) filled. Table: Contains surfactants and enzymes. Partial compositions [% by weight]

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• 2003
  • 2003-08-18 EP EP03792363A patent/EP1529006B1/de not_active Expired - Lifetime
  • 2003-08-18 JP JP2005501206A patent/JP4147244B2/ja not_active Expired - Fee Related
  • 2003-08-18 ES ES03792363T patent/ES2274311T3/es not_active Expired - Lifetime
  • 2003-08-18 WO PCT/EP2003/009135 patent/WO2004018319A1/de active IP Right Grant
  • 2003-08-18 AT AT03792363T patent/ATE341498T1/de active
  • 2003-08-18 AU AU2003264066A patent/AU2003264066A1/en not_active Abandoned
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